Cross-linkable compositions comprising an ethylenically unsaturated polymer and a sulfur dioxide addition product

ABSTRACT

The disclosed compositions contain an ethylenically unsaturated polymer and an addition product of sulfur dioxide with certain bicyclic tertiary amines, representative of which is triethylenediamine. The compositions may be cross-linked by the application of heat.

United States Patent Inventor Appl. No.

Filed Patented Assignee CROSS-LINKABLE COMPOSITIONS COMPRISING AN ETHYLENICALLY UNSATURATED POLYMER AND A SULFUR DIOXIDE ADDITION PRODUCT 11 Claims, No Drawings U.S.Cl

117/122 PA, 117/161 K, 117/161 R, 156/327,

156/338, 260/2 EP, 260/2 EC, 260/75 S, 260/75 UA, 260/78.4 R, 260/78.5 T, 260/79.3 R, 260/98,

' 51 Int.Cl ..c07d 51/70,

C08c 5/00, C08f 27/06 [50] Field of Search 260/268 8, 268 T, 22 A, 22 T, 98, 79.3 R, 78.5 T, 78.4 R, 769,

75 S, 75 UA, 2 EP, 2 EC, 77.5 AC, 862

[56] References Cited UNITED STATES PATENTS 3,1 12,320 11/1963 Farkas 260/268 3,169,992 2/1965 Henn.... 260/268 3,459,684 8/1969 Wilson 260/2 3,528,964 9/1970 Tesoro 260/231 Primary Examiner-Donald E. Czaja Assistant ExaminerRonald W. Griffin Attorney-John W. W lllSuI'l ABSTRACT: The disclosed compositions contain an ethylenical1y unsaturated polymer and an addition product of sulfur dioxide with certain bicyclic tertiary amines, representative of which is triethylenediamine. The compositions may be crosslinked by the application of heat.

product is a wherein Z is selected from the group consisting of the N and R-C radicals, each R is independently selected fromthe group consisting of hydrogen and C,C alkyl radicals, n is l when 2 is the R-C radical, and n is l or 2 when 2 is the N radical. Specific embodiments of the sulfur dioxide addition product of this invention include the sulfur dioxide adducts of quinuclidine, Z-methylquinuclidine, 2-ethylquinuclidine, 2- propylquinuclidine, 3-methylquinuclidine, 3-ethylquinuclidine, 4-methylquinuclidine, 2,6-dimethylquinuclidine, 3,5-dimethylquinuclidine, 2,2,6-trimethylquinuclidine, and 3- ethyl-3-methylquinuclidine, and the monoand di-(sulfur dioxide) adducts of l,4-diazabicyclo[2.2.2]octane, 2-methyll,4-diazabicyclo[2.2.2loctane, 2-ethyll ,4-diazabicyclo-[ 2.2.2]octane, 2-propyl-l,4-diazabicyclo[2.2.2]octane, 2,3- dimethyll ,4-diazabicyclo[2.2.2loctane, 2,5-dimethyll ,4- dia2abicyclo[ 2.2.2 ]-octane, 2,6-dimethyl-l ,4-diazabicyclo[ 2.2.2]octane, 2,5,7-trimethyl-l,4-diazabicyclo[2.2.2]octane, and 2,2,5,5,-tetramethyll ,4 aliazabicyclo[2.2.2]octane.

in general, these sulfur dioxide addition products are solid at -25 C. and have melting points substantially above 2025 C. Under anhydrous conditions and at 20-25' C. they are stable. However, water causes them to decompose, and at temperatures usually substantially above 20-25' C. slow thermal decomposition occurs. They are substantially insoluble at 20-25 C. in most organic solvents including acetone, methyl ethyl ketone, n-heptane, cyclohexane and toluene.

These sulfur dioxide addition products have utility as crosslinking agents for unsaturated polymers cross-linkable by sulfur dioxide. By admixing the sulfur dioxide addition product with a substantially uncross-linked, ethylenically unsaturated polymer, and establishing the temperature of the resulting mixture at a temperature at which takes place substantial thermal decomposition of the addition product, but not of the polymer, substantial cross-linking of the polymer is effected.

The sulfur dioxide addition products, except when with reference to formula I, n is l and Z is the N radical, also have utility in curable or cross-linkable, ethylenically unsaturated, polymer compositions which comprise a latent base and a precursor of, for example, a polyfunctional nitrile N-oxide or nitrile imine. Such compositions are useful as sealants, adhesives and coatings. A latent base is material which in the absence of water and/or heat is inert relative to the other components of the composition, but which, upon contact with water and/or upon the application of heat, provides alkaline substance that reacts with a precursor component, for example, one or more compounds having more than one hydroximoyl halide, carbonylnitrolic acid or hydrazide halide groups, of the composition to form a cross-linking agent, for example, one or more compounds having more than one nitrile N-oxide or nitrile imine groups, for the ethylenically unsaturated polymer component of the composition. In accordance with this invention, the addition products wherein there is an S0, component for each N radical forms part or all of the latent base in such compositions.

These products become effective alkaline substances in accordance with this invention either upon heating the compositions containing them or upon exposing such compositions to moisture.

Any unsaturated polymer, containing ethylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the ethylenic double bond, can be used in the compositions'of this invention. Where fluidized compositions are desired, unsaturated polymers having a molecular weight range of from about 1,000 to about 20,000 are preferred. However, higher molecular weight polymers can be used in conjunction with small amounts of solvents and/or plasticizers to obtain the desired fluidity. Typical unsaturated polymers than can be used are polybutadiene- 1,2, polybutadienel,4, styrene-butadiene copoylmers, isobutylene-isoprene copolymers, natural rubber, polyester resins such as maleateand fumarate-containing polyesters and polya'crylates, butadiene-acrylonitrile copolymers, ethylenepropylene-dicyclopentadiene terpolymers, polychloroprene, polyisoprene, unsaturated alkyd resins such as tall oil alkyd resins, polyether copolymers and terpolymers containing at least two unsaturated epoxide constituents such as propylene oxide-allyl glycidyl ether copolymers and ethylene oxideepichlorohydrinallyl glycidyl ether terpolymers, unsaturated urethane copolymers and blends of these polymers with each other. In some cases it may be desirable to use partially hydrogenated products of the above unsaturated polymer.

The precursor component utilized in those ethylenically unsaturated polymer compositions of this invention which depend upon formation of a polyfunctional nitrile N-oxide or nitrile imine to effect cross-linking is a polyfunctional hydroximoyl halide, carbonynitrilic acid or hydrazide halide. The polyfunctional hydroximoyl halides and carbonylnitrolic acids lead to formationof polyfunctional nitrile N-oxides, whereas the polyfunctional hydrazide halides lead to formation of polyfunctional nitrile imines. V

In general, the precursor component of the compositions of this invention is a compound selected from the group consisting of wherein Y is a substituent selected from the group consisting of halide and nitro, Z is a halide substituent, R is an organic radical having a valence greater than 1, generally 2 to 10 and preferably 2 to 6, and x is an integer-equal to the valence of R. The halide substituent may be fluoride, chloride, bromide or iodide. Also, R is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl and aralkyl, and R" is the same as R except that it can not be hydrogen.

Generally, R is selected from the group consisting of the hydrocarbon, halide substituted hydrocarbon, hydrocarbonoxy-hydrocarbon, hydrocarbon-thio-hydrocarbon, and hydrocarbon-sulfonyl-hydrocarbon polyvalent radicals. In preferred embodiments of this invention R is a divalent organic radical selected from the group consisting of alkylene radicals such as, for example, methylene, ethylene,- trimethylene, tetramethylene, pentamethylene, hex amethylene, octamethylene, decamethylene,

dodecamethylene and octadecamethylene; cycloalkylene radicals such as, for example, cyclohexylene, cyclopentylene, cyclooctylene and cyclobutylene; arylene radicals such as, for example, 0-, mand p-phenylene, naphthylene and biphenylene; arylene-dialkylene radicals such as, for example, 0-, mand p-xylylene diethylene and 0-. mand p-phenylene diethylene; alkylene-diarylene radicals such as, for example,

methylene bis(o-, mand p-phenylene) and ethylene bis(o-, mand p-phenylene); cycloalkylene-dialkylene radicals such as, for example, l,2-, 1,3- and l,4-cyclohexane-dimethylene and 1,2- and 1,3-cyclopentane dimethylene; and the alkylene oxy-alkylene radicals, arylene-oxy-arylene radicals, alkarylene-oxy-arylene radicals, alkarylene-oxy-alkarylene radicals, aralkylene-oxy-alkylene radicals, and aralkylene-oxyaralkylene radicals, as well as the corresponding thio and sulfonyl radicals, specific examples of which include methyleneoxymethylene, ethylene-oxy-ethylene, phenylene-oxy-phenylene, methylencphenylene-oxy-phenylenemethylene, phenylenemethylene-oxy-methylenephenylene, ethylene-thioethylene, phenylene-thio-phenylene, phenylenemethylenethio-methylene-phenylene and butylene-sulfonyl-butylene. The precursor of this invention also is inclusive of low molecular weight polymers having substituted along their chains about 2 to groups selected from the class consisting of hydroximoyl halide groups, carbonyl-nitrolic acid groups and hydrazide halide groups.

As mentioned earlier, R may be hydrogen, whereas R can not. Aside from this exception, R and R" may be the same and generally are selected from the group consisting of alkyl radicals containing one to carbon atoms, such as methyl, butyl, nonyl, decyl and pentadecyl; cycloalkyl radicals such as cyclopentyl, cyclooctyl and cyclododecyl; aryl radicals having 1 to 3 rings, such as phenyl, biphenyl and naphthyl; alkaryl radicals having C,C alkyl groups and l to 3 rings in the aryl group, such as methylphenyl and octadecylnaphthyl; and ma!- kyl radicals having C -C alkyl groups and l to 3 rings in the aryl group, such as benzyl and naphthylhexamethylene.

Exemplary of the polyfunctional nitrile N-oxides formed from precursors having the formula are the bis(nitrile N-oxides) such as terephthalo-bis(nitrile N- oxide), 2,3,5,6-tetramethylterephthalo-bis(nitrile N-oxide), isophthalo-bis( nitrile N-oxide), malono-bis(nitrile N-oxide), succino-bis-(nitrile N-oxide), glutaro-bis(nitrile N-oxide), 1,4-cyclohexane bis(carbonitrile N-oxide), methylenebis( p,p'-benzonitrile N-oxide methylene bis( m,m benzonitrile N-oxide), p-phenylene-bis(acctonitrile N-oxide), 4,4'-diphenylene-bis(carbonitrile N-oxide), and 1,5- naphthalene-bis(carbonitrile N-oxide); and polyfunctional nitrile oxides which have more than two nitrile oxide groups, such as l,3,5-benzene-tris(carbonitrile N-oxide), 1,5,7- naphthalene-tris(carbonitrile N-oxide), penta(acrylonitrile N- oxide), deca(crotononitrile N -oxide), as well as polyfunctional nitrile oxides such as 2,2'-oxybis(ethyl carbonitrile N-oxide), i.e., 2,2'-bis(carbonitrile N-oxide) diethyl ether, 4,4'-oxybis-(phenyl carbonitrile N-oxide), i.e 4,4'-bis(carbonitrile N- oxide) diphenyl ether, 2,2-thiabis(ethyl carbonitrile N-oxide) and 4,4'-thiabis(phenyl carbonitrile N-oxide). Precursors having the formula ((|3=NOH) are malonyl-bis(carbonitrile N-oxide), succinyl-bis(carbonitrile N-oxide), adipyl-bis(carbonitrile N-oxide), sebacylbis(carbo-nitrile N-oxide), l,2,3-propane-tris(carbonyl carbonitrile N-oxide), l,2,4-pentane-tris(carbonyl carbonitrile N-oxide), 1,4-cyclohexane bis(carbonyl carbonitrile N-oxide), p-phenylene-bis(acetyl carbonitrile N-oxides), 2,2- thiabis(acetyl carbonitrile N-oxide), 3,3-thiabis(propionyl carbonitrile N-oxide), isophthalyl carbonitrile N-oxide, terephthalyl carbonitrile N-oxide, 4,4'-bis-(benzoyl carbonitrile N-oxide), 4,4-methylenc-bis(benzoyl carbonitrile N-oxide), 4,4'-oxybis(benzoyl carbonitrile N-oxide), 3,3- thiabis(benzoyl carbonitrile N-oxide) and polymers containing pendant carbonitrile N-oxide groups, as for example, ethylene-acrylic acid copolymers and partially hydrolyzed poly(alkyl acrylate) where two or more of the pendant carboxyl groups have been converted to carbonyl carbonitrile N- oxide groups. Precursors of the formula lead to the formation of oxalyl-bis( carbonitrile N-oxide).

Exemplary of the polyfunctional nitrile N-oxides formed from precursors having the formula are, for example, the ethylene glycol, tetramethylene glycol, hexamethylene glycol, l,4-cyclohexene glycol, resorcinol, 4,4'-dihydroxybiphenylene and isopropylidene-4,4'-bisphenol esters of carboxy carbonitrile N-oxides.

Exemplary of the polyfunctional nitrile imines formed from precursors having the formula are bis(nitrile imines) such as -isophthalo-bis(N-phenylnitrile imine), terephthalo-bis(N-phenylnitrile imine), isophthalobis-(N-methylnitrile imine), terephthalo-bis(N-methylnitrile imine), isophthalo-bis(nitrile imine), terephthalo-bis(N-ethylnitrile imine, succino-bis(N-phenylnitrile imine), 1,4- and 1,3- cyclohexane-bis(N-phenylcarbonitrile imine), N,N'-bis(zenzylidene)-1,4-dihydrazinobenzene, and N,N -bis( benzylidene l ,3-dihydrazinobenzene; tetramethylene-bis(p-phenylene N-butyl carbonitrile imine); and polyfunctional nitrile imines having more than two nitrile imine substituents such as trimeso-tris(N-phenyl nitrile imine), trimeso-tris(N-methyl nitrile imine) and the corresponding tetraand hexa-substituted compounds derived from acids such as. 3,3,5,5'- tetracarboxybiphenyl and tris( 3 ,S-dicarboxyphenyl methane.

Illustrative of specific precursor components used in those compositions of this invention which depend upon formation of a polyfunctional nitrile N-oxide or nitrile imine are bis- (hydrazide chlorides) such as isophthaloyl-bis(phenylhydra-' zide chloride), terephthaloyl-bis(phenylhydrazide chloride), isophthaloyl-bis(methylhydrazide chloride), isophthaloylbis(ethylhydrazide chloride), terephthaloyl-bis(methylhydrazide chloride), succinoylbis(phenylhydrazide chloride), adipoyl-his( methylhydrazide chloride), p-phenylene dipropionyl-bis(methylhydrazide chloride), tetramethylene dibenzoylbis( butylhydrazide chloride), N,N-p-phenylene-bis( benzoyl hydrazide chloride), N,N'-m-phenylene-bis(benzoyl hydrazide chloride), glutaryl-bis(phenylhydrazide chloride), and l,4-cyclohexane dicarboxy-bis(phenylhydrazide chloride); and polyfunctional hydrazide chlorides containing more than two functional groups, such as trimesoyl-tris(phenylhydrazide chloride), trimesoyl-tris( methylhydrazide chloride) and trimesoyl-tris(ethylhydrazide chloride). These are all precursors to polyfunctional nitrile imines, but related precursors to polyfunctional nitrile N-oxides may be similarly illustrated.

Varied amounts of the unsaturated polymer, precursor and latent base can be employed, depending upon the degree of cross-linking desired and the nature of the unsaturated polymer. In general, the amount of nitrile N-oxide or nitrile imine precursor employed (based on the weight of the polymer) is from about 1 percent to about 30 percent, preferably from about 5 percent to about percent. The latent base, which is the sulfur dioxide addition product of this invention, is present in an amount generally sufficient to effect conversion of substantially all the precursor to the corresponding nitrile N-oxide or nitrile imine, preferably in excess by about 20 percent to about 100 percent of the amount required to effect conversion of substantially of the precursor to the nitrile N-oxide or nitrile imine.

The sulfur dioxide addition products of this invention are made by admixing under anhydrous conditions compounds having the formula wherein Z and R have the same means as in Formula I, and sulfur dioxide. Compounds of formula ll are known, and are either commercially available or can be made according to processes disclosed in the prior art. Sulfur dioxide reacts with compounds of formula ll, when 2 is the R-C radical, on a 1:1 mole basis. It reacts with compounds of formula II when Z is the N radical and n is 2 on a 2:] mole basis. In these two instances, it is preferred that the quantity of sulfur dioxide mixed with the compound or compounds be in stoichiometric excess. Sulfur dioxide reacts with compounds of formula II when 2 is the N radical and n is l on a 1:1 mole basis, and in this instance it is preferred that the quantity of sulfur dioxide admixed with the compound or compounds be substantially less than I mole per mole of the compound or compounds. The reaction takes place at 20-25 C., although higher and lower temperatures can be employed. It also occurs at atmospheric pressure, although higher and pressures can be used. Preferably, the reaction is effected in a relatively inert, anhydrous liquid reaction medium in which the reactants are soluble, but in which addition product is substantially insoluble. Examples of such a liquid reaction medium include benzene, toluene, hexane and methylene chloride, as well as mixtures thereof.

This invention is further illustrated by the following specific examples of various aspects of this invention, including preferred specific embodiments. In these examples, all parts and percentages are by weight, unless otherwise expressly indicated.

EXAMPLE I This example illustrates the synthesis of the di(sulfur dioxide) adduct of l,4-diazabicyclo[2.2.2loctane.

Twenty parts of l,4-diazabicyclol2.2.21octane, also known as triethylenediamine, was dissolved in 356 parts of tetrahydrofuran. One hundred parts of Linde 4A molecular 5C 17" IN %0 Calculated 30.0 8.0 I [.7 26.7 26.7 Found 3 l I 5.7 ".7 26.7 25.2

The yield of product was 30.6 parts.

Other di(sulfur dioxide) adducts and the sulfur dioxide adducts of compounds of formula ll when 2 is the R-C radical are made in similar fashion.

EXAMPLE 2 This example illustrates the synthesis of the mono(sulfur dioxide) adduct of l,4-diazabicyclo[2.2.2loctane.

Ten parts of l,4-diazabicyclo[2.2.2]octane was dissolved in 300 parts of anhydrous hexane. Three parts of anhydrous sulfur dioxide was added to this solution. A voluminous white precipitate formed immediately. The precipitate was removed from the reaction mixture by filtration in an inert atmosphere, and then was subjected to l5 millimeters of mercury vacuum at 25 C. until substantially all residual solvent was removed. The product thus obtained was a white powder. It was essentially the mono(sulfur dioxide) adduct of l,4-diazabicyclo[2.2.2]octane. The melting point of the product was l39.6-l 40.4 C. Analysis of the product showed:

so an 5S Calculated 41.0 as 15.9 1a.: Found 40.4 1.2 15.4 18.4

The yield of product was 7.5 parts.

EXAMPLE 3 Components Parts A a L. r polymer A Anhydrous terephthaloyl-bis( hydroximoyl chloride) 0.7

Di(sulfur dioxide) adduct of R-C l,4-diazabicyclol 2.2.2

octane The anhydrous cross-linkable ethylenically unsaturated sieve pellets was added to the resulting solution to remove any water that might be present. The mixture of pellets and solution was kept in a closed vessel for 20 hours at 20-25 C. The solution was decanted under nitrogen and then saturated with anhydrous sulfur dioxide gas. A precipitate formed. The precipitate was separated from the reaction mixture by filtration under nitrogen. The filter cake was then subjected for 2 hours at 20-25 C. to a vacuum of 0.3 millimeter of mercury to remove residual solvent.

The resulting product was a white crystalline powder. It was essentially the di( sulfur dioxide) adduct of 1,4-diazabicyclo[2.2.2] octane. it had a melting point of l73-l74- C. Analysis of the product showed:

polymer was a copolyester made by reacting l,000 parts of bis(hydroxy-ethoxyethyl) dimerate and parts of maleic anhydride. The crosslinkable polymer thus obtained had a molecular weight of 2,327, an acid number of 51.0, an ester number of 222.3, a hydroxyl number of 19.7, a fumarate ester content (calculated as fumaric acid) of 7.53 percent and a maleic ester content (calculated as maleic anhydride) of 4.91 percent. 1

The sealant composition of this formulation was made as follows. The anhydrous cross-linkable polymer and the anhydrous terephthaloyl-bis(hydroximoyl chloride) were dissolved in 17.8 parts of anhydrous tetrahydrofuran. The tetrahydrofuran was then removed in vacuo at 20-25 C. The resulting heavy oil and the di( sulfur dioxide) adduct were then milled together in a mortar under an inert atmosphere until a homogeneous cream was obtained. The cream itself could be stored at 20-2s c. in the absence of moisture for several months without curing. However, when the cream was exposed to the open atmosphere as a film of h-inch thickness, it cured integrally in 2 to 5 days.

Other compositions based on other di(sulfur dioxide) adducts of this invention and on the sulfur dioxide adducts of the compounds of formula ll where Z is the R-C radical can be made in similar fashion with the latter adducts preferably being used in twice the molar quantity of the di(sulfur dioxide) adducts.

EXAMPLE 4 This example illustrates another cross-linkable polymer sealant composition of the type employing a latent base.

Ditlulfur dioxide) adduct of l,4-dllzabicyclol 2.2.2loctane s The cross-linltable polymer in this formulation was the same as that described in example 3.

The sealant composition of this formulation was made by dissolving the cross-linkable polymer and the anhydrous isophthaloyl-bis(hydrazide chloride) in 50 parts of anhydrous tetrahydrofuran. removing the tetrahydrofuran under subatmospheric pressure at 20-25 C., and then admixing under a nitrogen atmosphere the resulting viscous oil with the di(sulfur dioxide) adduct until a homogeneous yellowish cream was obtained.

This composition could be stored in the absence of moisture for several months without curing. On the other hand, when cast as a film of 55-inch thickness and then exposed to the open atmosphere, it cured within 2 to 5 days to a rubber that was insoluble in tetrahydrofuran.

Other compositions based on other di(sulfur dioxide) adducts of this invention and on the sulfur dioxide adducts of the compounds of formula II where Z is the R-C radical can be made in similar fashion, with the latter adducts preferably being used in twice the molar quantity of the di(sulfur dioxide) adducts.

EXAMPLE 5 A mixture containing 40 parts of an ethylenically diunsaturated, linear urethane copolymer having a molecular weight of about 15,000, 4.6 parts of an ethylenically triunsaturated, branched urethane copolymer having a molecular weight of about 5,000 and [.6 parts of bis(phenyl glyoxylohydroximoyl chloride) was prepared by dissolving the components in anhydrous tetrahydrofuran and subsequently removing the solvent under reduced pressure. The mixture then was milled under an atmosphere of nitrogen with 1.7 parts of a di(sulfur dioxide) adduct of triethylenediamine prepared essentially according to the procedure of example 1 except to use previously dried reagents and omit the treatment with Linde 4A molecular sieve pellets.

The homogeneous, pasty composition obtained from the milling operation was stable on storage for several months. However upon exposure as film to 80 percent humidityat room temperature, the composition cross-linked to a rubber product which was insoluble in tetrahydrofuran. Also, samples of the composition heated to 1 C. for 3 minutes or to 150 C. for l minute cross-linked to tough rubber products insoluble in tetrahydrofuran.

EXAMPLE 6 This example illustrates utilization of the sulfur dioxide addition product of example 1 as a cross-linking agent for unsaturated polyester compositions.

The formulation of the unsaturated polyester composition of this example was:

Parts Components Unsaturated polyester Di(sulfur dioxide) adduct of lAdiazabicyclol2.2.2loctanc of the mixture at C. The resulting product was crosslinked, being insoluble in tetrahydrofuran. A sample of the polyester alone, when established and maintained for 2 hours under nitrogen at 170 C. remained soluble in tetrahydrofuran.

Other compositions based on other di(sulfur dioxide) adducts of this invention and on the sulfur dioxide adducts of the compounds of formula ll wherein Z is the R-C radical can be made in similar fashion, with the quantities of the latter adducts preferably being greater so that in each case they are about twice the molar quantity of the di(sulfur dioxide) adduct.

EXAMPLE 7 Parts Components Unsaturated polyester Monotsulfur dioxide) adduct of l .4-dlazubicyclol 2.2.2

loctsne The unsaturated polyester was a product made substantially as described in example I of U.S. Pat. No. 2,634,251 to Kass.

This composition in cross-linked condition was made by admixing the components in a closed vessel under nitrogen, and then establishing and maintaining for 2 hours the temperature of the mixture at C. The resulting product was crosslinked, being insoluble in common solvents for the uncrosslinked polyester, such as tetrahydrofuran, methylene chloride and methyl isobutyl ketone. Other compositions based on other mono(sulfur dioxide) adducts of this invention can be 'made in similar fashion.

What I claim and desire to protect by Letters Patent is:

1. A cross-linkable polymer composition comprising an unsaturated polymer containing ethylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the cthylenic double bond and a sulfur dioxide addition product having the formula wherein Z is selected from the group consisting of N and R-C substituents, each R is independently selected from the group consisting of hydrogen and C C, alkyl substitutents, n is I when Z is a R--C substituent and n is l or 2 when 2 is N.

2. The cross-linkable polymer composition of claim 1 containing precursor material which when contacted with alkaline substance forms a cross-linking agent for said polymer. said precursor material being a polyfunctional hydroximoyl halide, carbonylnitriolic acid or hydrazide halide, and wherein the sulfur dioxide addition product acts as a latent base.

3. The composition of claim 2 wherein the precursor material is a polyfunctional carbonylnitrolic acid.

4. The composition of claim 2 wherein the precursor material is a polyfunctional hydrazide halide.

5. The composition of claim 2 wherein the precursor material is a polyfunctional hydroximoyl halide.

6. The composition of claim 5 wherein the sulfur dioxide addition product is the di(sulfur dioxide) adduct of triethylenediamine.

7. A process for cross-linking an unsaturated polymer containing cthylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the cthylenic double bond which comprises heating said polymer in admixture with a sulfur dioxide addition product having the formula wherein Z is selected from the group consisting of N and RC substituents, each R is independently selected from the group consisting of hydrogen and C,C alkyl substituents, n is 1 when Z is a RC substituent and n is l or 2 when Z is N.

8. The process of claim 7 wherein the admixture of said polymer and said sulfur dioxide addition product contains a precursor material which when contacted with alkaline substance forms a cross-linking agent for said polymer, said precursor material being a polyfunctional hydroximoyl halide, carbonylnitrolic acid or hydrazide halide, and wherein the sulfur dioxide addition product acts as a latent base.

9. The process of claim 8 wherein the precursor material is a polyfunctional hydroximoyl halide and the sulfur dioxide addition product is the di(sulfur dioxide) adduct of triethylenediamine.

an unsaturated polymer containing ethylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the ethylenic double bond.

1 l. The process of claim 10 wherein the precursor material is a polyfunctional hydroximoyl halide and the sulfur dioxide addition product is the di(sulfur dioxide) adduct of triethylenediamine.

Patent No. U.. S.P. 3,627, 715 Dated December 14, 1971 Inventor) Karl Brack (Case 18-23) It is certified that error appears in the above-iientified patent and that said Letters Patent are hereby corrected as shown below:

5 Col, 5, Line 13 of p.p.; Page l0, Line 4 of space "substantially of should be "substantially all of" Col; 5, Line 2'7 of 13910.; Page 10, Line 12 of spec.

"means" should be "meanings" Col 5, Line 4-3 of p.p.; Page l0, Line 27 of spec.

"higher and pressure" should be "higher and lower pressure" Col. 6, Line 27 (agiproxfi of p.p. 7 Page 12, Line ll of spec.

0C %N %S shoulcl foe "%C %l-I %l l' %S" Col '6, Line 45 (apioroxfi of pup Page l2, Line 26 of spec.

"of R-C 1,4" should be "of l,4--"

col 8, Line 6i of 3gp. Claim 2, Line 4 5 of spec "carioonylnitriolic" should. be carhonyinitrolic" Col; 10 of pop Claim 10, last 3 lines an unsaturated polymer containing ethylenic wherein there is at least one hydrogen rafiical attached to at least one of the carbon atoms of the ethylenic double bond,

-- should read "wherein Z is selected from the group consisting of N ene R ef; selostituents, each R is independently selected firom the group consisting of hydrogen anrl (Zr-C3 alkyl substituents, n is l when Z is a substituea'lt and n is l or 2 when 2 is No Signed and sealed this 23rd day of May 193 2,

(SEAL) Attest:

EDWARD MQFLETGHER 5R0 ROBERT GOTTSGHALK Attesting Officer Commissioner Patents 

2. The cross-linkable polymer composition of claim 1 containing precursor material which when contacted with alkaline substance forms a cross-linking agent for said polymer, said precursor material being a polyfunctional hydroximoyl halide, carbonylnitrolic acid or hydrazide halide, and wherein the sulfur dioxide addition product acts as a latent base.
 3. The composition of claim 2 wherein the precursor material is a polyfunctional carbonylnitrolic acid.
 4. The composition of claim 2 wherein the precursor material is a polyfunctional hydrazide halide.
 5. The composition of claim 2 wherein the precursor material is a polyfunctional hydroximoyl halide.
 6. The composition of claim 5 wherein the sulfur dioxide addition product is the di(sulfur dioxide) adduct of triethylenediamine.
 7. A process for cross-linking an unsaturated polymer containing ethylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the ethylenic double bond which comprises heating said polymer in admixture with a sulfur dioxide addition product having the formula
 8. The process of claim 7 wherein the admixture of said polymer and said sulfur dioxide addition product contains a precursor material which when contacted with alkaline substance forms a cross-linking agent for said polymer, said precursor material being a polyfunctional hydroximoyl halide, carbonylnitrolic acid or hydrazide halide, and wherein the sulfur dioxide addition product acts as a latent base.
 9. The process of claim 8 wherein the precursor material is a polyfunctional hydroximoyl halide and the sulfur dioxIde addition product is the di(sulfur dioxide) adduct of triethylenediamine.
 10. A process for cross-linking an unsaturated polymer containing ethylenic unsaturation wherein there is at least one hydrogen radical attached to at least one of the carbon atoms of the ethylenic double bond which comprises exposing to moisture said polymer in admixture with a precursor material which when contacted with alkaline substance forms a cross-linking agent for said polymer, said precursor material being a polyfunctional hydroximoyl halide, carbonylnitrolic acid or hydrazide halide, and a latent base which is a sulfur dioxide addition product having the formula
 11. The process of claim 10 wherein the precursor material is a polyfunctional hydroximoyl halide and the sulfur dioxide addition product is the di(sulfur dioxide) adduct of triethylenediamine. 